Process of producing fast printings



May 16, 1932 TATES ARTHUR ZITSCHER AND ,FRANZ MURIS, OF OFFENBAGH-ON-THE-WIAIN, GERMANY,

ASSIGNORS TO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A. CORPORA- TION OF DELAWARE I PROCESS OF PRODUCING FAST PRINTING-S No Drawing, Original application filed December 8, 1925, Serial No. 74,148. Patent No. 1,737,905, dated December 3, 1929, and in Germany December 25, 1924. Divided and this application filed April 29,

1929. Serial No. 359,168.

This application is a division from our application SerialNo. 74,148, filed Dec. 8, 1925.

Our invention relates to a new process of producing fast printings consisting in fixing mixtures containing alkali metal salts of azo components adapted for producing azo dyestuffs on the fiber and salts of sulfnitrosaminic acids of the general formula:

Aryl (N NO SOiMe n,

wherein R andR" represent aromatic radicals, Me nieansan alkali metal and 7 stands for one of the numbers 1 and 2.

Such a development may be executed by treating the goods with acid vapors or by passing them in a bathcontaining a feeble acid, for instance a feeble organic acid such as formic acid, "or bypassing them in two baths the first of which contains an acid or an acid salt. the second bath contains salts of feeble acids, such as formates or acetates, or an alkali. The process is each time to be adapted to the character of the sulfnitrosaminic acid in question.

In this manner printings completely fast to washing are pi'oduced, the azo dyestuffs, thus formed, nojlongercontaining the sulfonic group of/the,sulfnitrosaminic acids, which are their basis.

Regarding the well known instability of the sulfnitrosaminic salts, especially in the (ll statP see Ber. (l. Chem. (lies, vol. 28, page 31(5-l, and vol. 30, pages 870, 874 and SSW-it appears to be very surprising, that the sulfnitrosaminic salts, when mixed with the .less than 3,.

alkali metal salts of the azo-components can withstand the process of drying and steamn being a number less than three and Me meaning an alkali metal, and of alkali nitrite, which forms the corresponding sulfnitrosaminic acid by treating subsequently with an acid substance, together with an al kali salt of the azo component being used for printing.

Among the salts of sulfnitrosaminic acids of arylamines those of arylamines, having a substantive character, may be emphasized such as for example those of aminoor diamino compounds of the diaryl series or of the aromatic series, containing an azo-, azoxy-, urea-, thiazol-, imidazol-, pseudoazimino or a similar group. Especially valuable printings are obtained by using salts of sulfnitrosaminic acids of aminoazo bodies of the general? formula:

wherein R and R mean aromatic residues and'Me meaning an alkali metal, which may be substituted or not, and a means a number As azo components adapted for producing azo dyestuffs on the fiber the naphthols and their derivatives may be named, such as B- naphthol and its derivatives, such as acyl-- aminonaphthols, for example the benzoylaminonaphthols and the arylides of 2.3-hydroxynaphthoic acid, the derivatives of 1- hydroxynaphthalene-4-carboxylic' acid, as described in U. S. A. Letters Patent No. 1,453,660 and bodies containing a methylene group. capable of combining, for example the pyrazolone derivatives or derivatives of B- ketonaldehyde, such as the acylacetic acid arylides, the diand monoacylacetoarylamines, as described in the French Letters Patent No. 567 ,284 and others. v

- The production of the sulfaminic acids and of their nitroso compounds respectively may be executed according to the process, as described in Ber. d. Deutschen Chem. Gesellschaft, vol. 28, page 3160 and vol. 30, page 880, and vol. 50, page 1117, respectively.

The new printing colors may be used for the multi-color printing besides the known nitrosamine printing colors.

The following examples illustrate the invention, the parts being by weight and all temperatures given being centigrades.

Elia-ample; 1

21.5 grs. of the sodium salt of dehydrothiotoluidinesulfaminic acid of the formula (of 80% strength), are dissolved in 150 grs. of hot water. After cooling down by adding 14. 5 grs. of hydrochloric acid(d=1.160) the free sulfaminlc-acid is separated. By adding a solution 4 grs. of nitrite of sodium in 14 grs. of water the sulfnitrosaminlc acid is formed. By

pouring in 2O grs. of caustic soda solution (35 B.)

224 grs. of a paste are obtained.

225 grs. of this paste are worked up with 7. 2 grs. of B-naphthol. 14. 8 grs. of caustic soda solution (35 B.). grs. of Turkey red oil, 208 grs. of water and 500 grs. of neutral starch tragacanth thickening to 1000 grs. of a printing paste.

The goods are printed, dried, steamed for 3 minutes, passedthrough a bath of 80 containing 20 grs. of acetic acid of 8 B. in the liter, rinsed, soaped, rinsed and dried.

A yellowish-red print is obtained.

Example 2 '15 grs. of 5-nitro-2-anisidine-sulfaminic acid of the formula:

OCH:

NH-SO Na OzN {he sodium salt 0! 90%01! strength, are dissolved 142 grs. of hot water, after cooling down by adding 14. 5 grs. of hydrochloric acid (d=1.160) t e free suliciiiminip acid is separated. By adding a soluon o 4 grs. of nitrite of sodium in 15 grs. of water the sultnitrosaminic acid is formed.

By adding 19. 5 grs. of caustic soda solution of 35 Be, 210 grs. of a paste are obtained.

210 grs. 15 grs. 15 pzrs.

260 grs.

500 grs.

1000. grs. of a-printing paste.

The cotton, goods are printed, dried, steamed for 3 minutes in a rapid steam-apparatus at 100-1059, then passed through a cold bath, containing 200 grs. of hydrochloric acid (d=1.160) in the liter, rinsed and passed again at through a bath containof this paste are worked up with of a a-naphthalid of 2-3- x aphthoic acid, of caustic soda solution of 85' B.,

of water and of a neutral starch tragacanth thigkening to ing 50 grs. of acetate of sodium in the liter,

rinsed, soaped, rinsed again and dried.

In this manner a red likeclaret print is obtained.

Example 3 20. 5 grs. of the sodium salt of meta-aminoazotoluenesulfaminic acid of the formula:

v Q-N; Nn4oim CHI 0 I (of 80% of strength) are worked up with 15 grs. ldot meta-nitranilide oi 2-3-hydroxynaphthoic 19. 7 grs. of caustic soda solution of 35 B.,

3. 8 grs. of nitrite of sodium,

45 grs. ofTurkey red oil, 396 grs. of water and 500 grs. of a neutral starch tragacanth thickening to 1000 grs. of printing paste.

The unprepared cotton goods are printed, dried, steamed for 3 minutes, passed through a hot bath of 90 containing 50 grs. of formic acid and 50 grs. of common salt in the liter, rinsed, soaped, rinsed again and dried. v

A garnet-like print is obtained.

Example 4 84 grs. of a paste of 50% oi. strength oi. the salt of phenego]azo-1-naphthylsulfnitrosaminic acid of the ormu a:

. NO soava OCgHl (pre ared according to Ber. d. Deutsch. Chem. Ges. vol 8, page 3164, and vol. 50, page 1117, respectively) are worked up with 31 grs. of 2-8-hydroxg'naphthoyl-meta-nitraniline,

grs. of Turkey-re oil,

grs. of caustic soda solution of 36 B.,

grs. of water and grs. of a neutral starch tragacanth thickening to grs. oi! a printing paste.

Example 5 grs. of the sodium salt of ortho-anis0l-azo-1- naphthylsulfamic acid oi. the formula:

=N8NHBOaNL OCH;

, 1 of 80% of strength are made up with 26.5 grs of the anllide of 2- 3-hydroxynaphthoic acid,

10. 5 grs. of nitrite of sodium,

50 grs. of Turkey-red 'oil, 30 grs. of caustic sodium solution of 36 B.,

336 grs. of water and 500 grs. of a neutral starch tragacanth thickening to 1000 grs.

The goods are printed, dried, steamed and passed through an acid and alkaline bath, as described in Example 4.

A reddish-black print is obtained.

Example 6 14.5 grs. of the sodium salt of nieta-meta'edichlorobenzidinedisulfaminic acid of the formula:

of 80% or strength are worked up with grs. igf meta-nitranilide of 2-3-hydroxynaphthoic ac 19. 7 grs. of caustic soda solution of 85 B.,

3. 8 grs. of nitrite of sodium, 45 grs. of Turkey-red oil, 402 grs. of water and 500 grs. of a neutral starch tragacanth thickening to 1000 gi's. of a printing paste.

The unprepared cotton goods are printed, dried, steamed for 3 minutes and developed in a bath, as described in Example 3.

A bluish-red print is obtained.

Example 7' 21.5 grs. of the sodium salt of dehydrothiotoluidinesulfaminic acid .of 80% of strength are work ed up with 33 grs. of the anilide of 2'3-hydroxynaphthoic acid; 19. 7 grs. of caustic soda solution of 35 B.,

3'. 8 grs. of nitrite of sodium, 45 grs. of Turkey-red oil, 397 grs. of water and 500 grs. of a neutral starch tragacanth thickening to 1000 grs. of a printing paste.

The cotton goods are printed, dried, steamed for 3 minutes, passed through a cold bath containing 50 grs. of sulfuric acid of 66 B. in the liter, rinsed and passed at about 50 through a bath containing 50 grs. of formats of sodium in the liter,"rinsed, soaped, rinsed again and dried.

A red-like claret print is obtained.

Example 8 21. 5 grs. of the sodium salt of dehydrothiotoluidinesuiltflzliminic acid of 80% of strength are worked up w 12. 5- rs. of 4-11ydroxvnaphthylphenylketone,- 21s. of caustic soda solution of B.,

4 grs. of nitrite of sodium, grs. of Turkey-red oil, 397 grs. of water and 500 grs. of a neutral starch tragacanth thickening to 1000 grs. of a printing paste.

Example .9.-Two-colo'rprinting ((1) Printing color for black:

49 grs. of the sodiumsalt oi. ortho-phenetol-azo-lnaphthylsulfaminic acid of 80% of strength are made up with g 31 grs. of 2-3-hydroxynaphthoyl-meta-nitraniline, 10. 5 grs. of nitrite of sodium, grs. of Turks -red oil,

30. 5 grs. of caust c soda solution of 36 B.,

329 grs. of water and 500 grs. of a neutral starch tragacanth thickening to 1000 grs.

(6) ,Printing color for red:

120 grs. of a paste containing 15% ot the anilide of 2-3hydroxynaphthoic acid, a. nitrosamine alkali metal salt of 3-nitro-L4'toluidine and free caustic soda solution, are mixed with 40 grs. of Turkey-red oil,

100 grs. of a solution of a neutral chromatc 1 4,

240 grs. of water and 500 grs. of a neutral starch tragacanth thickening to 1000 grs.

The goods are printed with the preceding colors, dried, steamed at 100 for 5 minutes with steam containing acetic acid, then passed broadly through a bath containing 30 grs. of sodium bisulfate in the liter, rinsed, subsequently passed through an alkaline bath and worked up in the usual manner.

A two-color print, a beautiful black besides red is obtained.

We claim:

1. In a process of producing fast printings the step comprising developing the dyestufi by reacting with an acidic substance upon a textile material impregnated with an alkali metal salt of a coupling compound suitable as' developer in the art of producing azo dyestufl's on the fiber, and a salt of a sulfnitrosaminic acid of the general formula:

in which R and R" are aromatic radicals,

Me means an alkali'metal and n a numeralless than 3.

2. In a process of producing fast printings the step comprising printing upon a textile material an alkali metal salt of a coupling compound suitable as developerin the art of producing azo dyestulis on the fiber, and a salt of a sulfaminic acid of the general formula;

in which R and R" are aromatic radicals, Me means an alkali "metal and n a numeral less than 3, transforming the sulfaminic acid compound into the corresponding sulfnitrosaminic acid compound on the material and reacting with an acidic substance upon, the so treated material.

3. In a process of producing fast printings the step comprising printing upon a. textile material an alkali metal salt of a coupling compound suitable as developer in the art of producing azo dyestufis on the fiber, an alkali metal nitrite, and a salt of a sulfaminic acid of the general formula:

H T N=NTR '[N tmMe] n in which R and R" are aromatic radicals, Me means an alkali metal and n a numeral less than 3, and reacting with an acidic substance upon the so treated material to proby reacting'with an acidic substance upon ain which R and R" are aromatic radicals, Me means an alkali metal and n a numeral less than 3. 5. In a process of producing fast printings the step comprising printing upon a textile material an alkali metal salt of .a 2.3-hydroxynaphthoic acid arylide, and a salt of a sulfaminic acid of the general formula i in which R and R" are aromatic radicals, Me means an alkali metal and n a numeral less than 3, transforming the sulfamimc acid compound into the corresponding sulfnitrosaminic acid compound on the material and reacting with an acidic substance upon the so treated material.

6. In a process of producing fast printings the step comprising printing upon a textile material an alkali metal salt of a 2.3-hydroxynaphthoic acid arylide, an alkali metal nitrite and a salt of a sulfaminic acid of the general formula:

in which R and R" are aromatic radicals,

Me means an alkalimetal and n a numeral less than 3, and reacting with an acidic substance upon the so treated material to produce the corresponding sulfnitrosaminic acid v compound and to develop the dyestuif.

7. In a process of producing fast printings the step comprising developing the'dyestuif textile material impregnated with an alkali metal salt of 2.3-hydroxynaphthoic-meta nitranilide and a salt of phenetol-azo-lnaphthyl sulfnitrosaminic acid.

8. As new compositions of matter printing pastes comprising an alkali metal salt of a coupling component suitable as developer in the art of producing azo dyestuffs on the fiber and a salt of a sulfnitrosaminic acid of the general formula whereinfR and R" represent aromatic radicals, Me means an alkali metal and n stands for. one of the numbers 1 and Z 9. As new compositions of matter printing pastes comprising an 'alkali metal salt of a 2.3-hydroxynaphthoic acid arylide and a salt of a sulfnitrosaminic acid of the general forwherein R and R" represent aromatic radiwherein R and R" represent aromatic radicals,, Me means an alkali metal and n stands for one of the numbers 1 and 2.

11. As new compositions of matter printing pastes comprising an alkali metal salt of a 2.3-hydroxynaphthoic acid arylide, an alkali metal nitrite and a salt of a sulfaminic acid of the general formula:

wherein R and R" represent aromatic radi cals, Me means an alkali metal and n stands for one of the numbers 1 and 2.

12. As a new composition of matter a printing paste containing about 31 parts of 2.3- hydroxynaph'thoic acid meta nitranilide, about 30 parts of caustic soda solution of 36 B., about 84 parts of a paste of 50% strength of the sodium salt of phenetol-azo-l-naph thyl-sulfnitrosaminic acid, about 50 parts of Turkey-red oil, about 50 parts of water and about 500 parts ofneutral starch tragacanth thickening.

In testimony whereof we afiix our signatures.

ARTHUR ZITSCHER. FRANZ MURIS. 

